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Reactivity Study on Nonheme Oxoiron(IV) Intermediates by Tuning the Equatorial Ligands

Title
Reactivity Study on Nonheme Oxoiron(IV) Intermediates by Tuning the Equatorial Ligands
Authors
김수희
Issue Date
2008
Department/Major
대학원 나노과학부
Publisher
이화여자대학교 대학원
Degree
Master
Abstract
Heme과 nonheme 철 효소의 선택적인 biotransformations에서 high-valent oxoiron(IV) 중간체가 활발한 산화 중간체임이 밝혀져 왔다.1 또한 heme 철 효소에서 cyteine (cytochrome P450), tyrosine (catalase), histidine (peroxidase)와 같은 proximal 리간드들이 oxoiron(IV) 중간체의 반응성이나 안정성에 중요한 역할을 담당하는 것으로 알려져있다.2 따라서 본 논문에서는 nonheme oxoiron(IV) 화합물의 equatorial 리간드에 의한 화학적 성질의 변화를 연구해 보고자 하였다. 본 논문에서는 nonheme iron(II) 화합물인, [Fe^(II)(BPMEN)-(OTf)₂] [BPMEN = N,N’-bis(2-pyridylmethyl)-N,N’-dimethyl-trans-1,2-diaminoethane]를 사용하였다. [Fe^(II)(BPMEN)(OTf)₂]에 peracetic acid를 첨가하여 oxo 중간체를 생성시켰으며, oxo 중간체의 equatorial 위치를 변화시킴에 따라 어떤 반응성의 차이가 발생하는지 관찰하였다.;High-valent oxoiron(IV) intermediates have been identified as the active species in selective biotransformations in heme and nonheme enzymes. In case of enzymes, the proximal ligand plays a crucial role in the stability and reactivity of the oxoiron(IV) intermediates. To explore this, we have prepared a nonheme iron(II) complex, Fe^(II)(BPMEN)(OTf)₂, and its oxo complexes by the addition of peracetic acid. The reactivity studies have been explored with alcohol oxidation, C-H activation, sulfoxidation and aromatic ring hydroxylation.
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일반대학원 > 화학·나노과학과 > Theses_Master
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